聚合物口模牵伸工艺研究进展

本文介绍了一种新的聚合物自增强工艺—口模牵伸工艺的发展及研究现状。与传统的拉伸辊牵伸、静压挤出及柱塞式挤出工艺相比,口模牵伸具有明显的优越性和发展潜力。     

Development of continuous die drawing production process for engineered polymer cores for wire ropes

Abstract

The process of continuous die drawing has been adapted as the means of production of polymer cores for wire ropes. The cores have a precisely engineered cross-sectional shape, which is produced by the die drawing process. In order to control this shape accurately, the drawing is carried out in two stages, first drawing in a heated circular conical die and secondly in a cooled fluted conical die. A production line has been developed, which produces core at commercially acceptable rates and with precisely controlled dimensional and mechanical properties. The polymer core serves as a replacement for the three strand cores made from natural fibres.     

Structure evolution and orientation mechanism of isotactic polypropylene during the two‐stage solid die drawing process

High oriented isotactic polypropylene prepared by self‐designed two‐stage die drawing apparatus was explored through kinds of methods, including differential scanning calorimetry, two‐dimensional wide‐angle X‐ray diffraction, polarized light microscope, and tensile test. The results showed that there was a great difference between the orientation mechanism and structure evolution of two‐stage solid die drawing process and single‐stage solid die drawing process. All samples would undergo free drawing process after die drawing process. Die drawing and free drawing process were of equal importance to single‐stage die drawing process while die drawing process showed an prominent contribution to the two‐stage die drawing process. Drawing speed showed beneficial influence on die drawing process for both single‐ and two‐stage die drawing process routes. Under the same processing condition, tensile strength and modulus of samples prepared by two‐stage die drawing process were higher than those prepared by single‐stage die drawing process and the maximum value could reach 241.93 MPa and 3.57 GPa, respectively. Moreover, two‐stage die drawing samples showed better dimensional stability than single‐stage die drawing samples especially under low draw rate. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46581.     

Analytical and experimental study of the die drawing of circular rods through conical dies

An analysis is presented of the process of die drawing isotropic polymers, in the form of circular rods, to produce highly oriented materials with enhanced mechanical properties. The stresses in a small element of material undergoing the drawing process have been analyzed using a force-equilibrium approach and the initial yield and flow stresses in the material have been predicted from the von-Mises yield criterion. The stress-strain-strain rate characteristics of the polymer used in the analysis were deduced from uniaxial tensile test data obtained at the same temperature at which the die drawing occurred. Experimental results are presented of the stress in polypropylene GSE-108 rods when die drawn at 90°C in a purpose-built die drawing facility. Novel techniques were used to determine the stress and strain distributions along the die. A comparison of the experimental results and the analytical predictions shows good agreement.     

Manufacture of ultrahigh-modulus poly(oxymethylenes) by die drawing

A stable experimental die drawing process has been operated for poly(oxymethylene) over a range of temperature. Rods possessing room-temperature Young's moduli up to 23 GPa were produced using a homopolymer grade, the values obtained from a copolymer being somewhat lower. This compares favorably with the best modulus achieved by hydrostatic extrusion but is rather lower than that produced by conventional drawing; reasons for this are discussed. A stable die drawing process has also been operated for glass fiber-reinforced poly(oxymethylene), but extensive macroscopic void formation occurred in the products under all conditions, reducing their potential for practical application.     

Drawing of polymers through a conical die

A new process is described in which ultra-oriented polymers are produced by drawing a billet of initially isotropic polymer through a converging die. The process, called die-drawing, has been used to make oriented polypropylene rods with room temperature Young's moduli up to 20.6 GPa. The considerable advantages of this process compared with conventional tensile drawing and hydrostatic or ram extrusion are discussed.     

A numerical study on warm deep drawing of polypropylene

Warm deep drawing of polypropylene, a semi-crystalline thermoplastic polymer, is studied using finite element analysis. In this process, a circular polypropylene blank is preheated to a temperature much below its melting temperature and deep drawn into the shape of a flat-bottom cylindrical cup using a punch-die combination, both initially at 25°C. The material model used for the analysis considers the effects of varying temperature and strain rate during the deep drawing process on the depth of draw. The effects of blank holder force, initial blank temperature, blank diameter, and die and punch corner radii on the depth of draw are determined. Thickness, temperature, and strain variations in the drawn cups, punch forces, and failure modes are also determined.     

口模拉伸过程PP/CaCO3复合材料结构演变及机理

利用口模拉伸法制备了轻质、高强、高模的聚丙烯（PP）/碳酸钙（CaCO₃）复合材料，分析了口模拉伸对材料微观结构、晶体结构、热性能和密度的影响，揭示了口模拉伸过程中材料结构演变及其机理。结果表明，随着拉伸过程的进行，材料内的原始球晶向微纤状晶体转变，同时发生晶粒细化现象，结晶度增大表明存在拉伸诱导结晶现象。微孔尺寸的显著增大及材料密度的显著降低主要发生在材料离开收敛流道壁面后的自由拉伸过程中。     

Dynamics of air drawing in the melt blowing of nonwovens from isotactic polypropylene by computer modeling

The dynamics of stationary air drawing in the melt blowing of nonwovens were determined on the basis of a single‐filament model in a thin‐filament approximation that accounts for polymer viscoelasticity, heat of viscous friction in the polymer bulk, and surface energy. Predetermined distributions of the air velocity and temperature along the melt blowing axis were assumed. Axial profiles of the polymer velocity, temperature, elongation rate, filament diameter, tensile stress, and extrapressure were computed for the melt blowing of isotactic polypropylene. The effects of the air‐jet velocity, die‐to‐collector distance, and polymer molecular weight are discussed. We predicted that the filament attenuation and velocity at the collector located in the air‐drawing zone would increase with increasing die‐to‐collector distance. The air‐drawing zone was shorter for higher air velocities and lower molecular weights. No online crystallization was predicted before the achievement of the collector, and melt bonding of the filament in the web should have occurred during cooling on the collector, accompanied by spherulitic crystallization. Significant online extrapressure in the filament was predicted in the case of supersonic air jets as resulting from polymer viscoelasticity, which could have led to longitudinal splitting of the polymer into subfilaments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fabrication of reinforced and toughened poly(lactic acid)/poly(butylene adipate-co-terephthalate) composites through solid die drawing process

In this study, poly(butylene adipate-co-terephthalate) (PBAT) was introduced to poly(lactic acid) (PLA) matrix to improve its inherent poor toughness. Besides, the orientation structure was also introduced via die drawing process to compensate for strength loss. The results indicate that die drawing process contributes to improve the mechanical properties of PLA. The tensile strength, modulus, and elongation at break of die-drawn pure PLA increased by 76.6, 36.1, and 1,375.0%, respectively, compared with those of isotropic PLA. Moreover, the tensile strength can be further improved by the addition of PBAT. The die drawing process can remarkably improve crystallinity, and the orientation factor is high when the PBAT content is less than 30 wt%. By combining the PBAT with highly oriented structure imported by die drawing process, it is possible to prepare simultaneously reinforced and toughened materials, which provides a new insight into the modification of PLA.     

Optimization of fiber drawing processes in terms of the filament state variables

A new method of optimizing the fiber drawing process involving the feed roll, the heated elements and the take-up roll is presented. In this method, the process is described in terms of the filament temperature and filament extension in the drawing zone. This is in contrast to the conventional approach in which the machine control variables such as the heated element temperature, fiber feed velocity and the total draw ratio were used to describe the process. It is shown that the drawing process seldom proceeds by a simple yielding mechanism and that a one-step drawing process usually involves a yield draw followed by a post-yield stretching. Using the drawing of nylon 6 fibers as an example, it is shown that the most critical factors related to achieving the highest fiber strength in drawing from a given precursor are the yarn temperature and yarn extension at yielding and during the post-yield drawing.     

游动芯头拉拔模具受力和温度分布的数值模拟

本文采用非线性有限元软件对铜管游动芯头拉拔工艺进行了数值模拟和分析研究,得出了铜管与模具接触面的法向力和摩擦力的分布规律;拉拔过程中的温度分布;从而推断出游动芯头发生粘铜和局部崩裂的主要原因。     

Drawing of nylon-6 by the novel incremental drawing process

Multifilament nylon-6 fibers are drawn by the novel incremental drawing process as well as by the conventional drawing process. In this process the fibers are stretched in 36 stages along the surface of two corotating cones fitted on the incremental drawing machine. Fibers are obtained from each stage, and from their diameter measurements it is shown that they are stretched in a predicted manner. Mechanical properties, as measured by Instron and by a sonic modulus tester, show higher tenacity and modulus values for the incremental process than for the conventional one at equivalent draw ratios. Structural properties are analyzed by density measurements, wide angle X-ray diffraction and birefringence. These showed higher crystallinity and higher crystalline as well as amorphous orientation factors for the incremental process at equivalent draw ratios. The mechanical property results are explained on the basis of structural development during drawing. It has been shown that the incremental drawing process is a suitable technique for obtaining superior properties in fibers and has commercial potential.     

Damage in large scale solid state deformation of thermoplastic polymers at elevated temperatures and varying strain rates

Abstract

A key factor which limits the production speed of the polymer die drawing process is the premature fracture of the material on exit from the die. In this paper, the growth of damage in the material during the die drawing process has been studied using a combination of thermoplastic finite element analysis and structural characterisation by means of scanning electron microscopy and small angle X-ray scattering for the specific case of die drawing of polyoxymethylene. It is demonstrated that special profiled dies offer a more beneficial strain rate distribution than the conventional conical dies and allow higher production speeds to be obtained. Voids grow in the material as a result of the tensile stresses pertaining near the die exit and then, crazes appear from within the material at a critical stress level leading ultimately to final fracture. The results suggest that although the crazes initiate at a critical stress, the extent of crazing at the maximum draw ratio obtained (～13) is independent of the type of die and hence the stress level. Fracture of the drawn product occurs at different stresses for different die profiles but always at the maximum draw ratio of 13, suggesting that this relates to the limiting extensibility of a molecular network.     

Novel CO2 laser drawing of thermotropic liquid crystal polymer and poly(ethylene 2,6‐naphthalate) blend fibers

Thermotropic liquid crystal polymer (TLCP)/poly(ethylene 2,6‐naphthalate) (PEN) were prepared by a melt blending, and were melt spun by a spin‐draw process. In this study, we suggest novel drawing technology using the CO₂ laser that can directly and uniformly heat up fiber inside to prevent the formation of ununiform structures in conventional heat drawing process. The properties of the heat/laser drawn TLCP/PEN blend fibers were superior to those of any other handled fibers, and were rather more excellent than those of TLCP/PEN blend fibers annealed at 135°C for 10 min. It was confirmed that the CO₂ laser drawing made it possible to achieve the optimal drawing effect by draw ratio. The combined heating and CO₂ laser‐drawing method has a great potential for industrial applications as a novel fiber‐drawing process, and it can also be applied continuously to conventional spin‐draw system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 205–211, 2007     

Shape changes during drawing of non-circular extruded profiles

Deformation during cooling and take-up of rectangular, triangular and T-shaped profiles were investigated. Experimental results show that there is an excellent agreement between changes in a cross-section dimension and prediction from the theory for various take-up speeds. The correlations decrease in the case where other process variables such as different melt temperatures and output rates are involved. Based on undrawn sample measurements, it has been concluded that to a high degree of approximation only a scaled-down change in shape occurs along the drawing path after die swell is completed. Industrial practices in handling profiles during cooling and take-up which may cause deviations from geometrically similar deformation were examined. Metal guides and local cooling by small water streams along the drawing path were used to impose shear forces on the profile. It was found that the effects of such shear forces has been small in comparison with the effects of elongational stress as indicated by only slight, if any, deviation from geometrically similar changes in cross-sections. Based on the data obtained, it is concluded that feedback control during profile drawing to give correct size is feasible based on monitoring a single dimension. The correct shape can, however, be obtained only by choice of the proper die geometry and other extrusion conditions.     

拉伸对聚芳砜酰胺(PSA)纤维力学性能的影响

研究了聚芳砜酰胺(PSA)纤维制备过程中各阶段拉伸倍数对纤维最终力学性能的影响,并制备出最高断裂强度达到3.62 cN/dtex的PSA纤维。要得到综合力学性能较高的PSA纤维,合适的表观喷头拉伸倍数为-50%～30%、塑化拉伸倍数为2、热拉伸倍数为2。PSA为较难结晶的高聚物,不论是聚合物粉末还是拉伸纤维,其结晶度都较低。PSA纤维的大分子取向与纤维的断裂强度关系十分密切,大分子取向因子与纤维的断裂强度呈线性关系,提高大分子取向程度是提高PSA纤维强度的重要途径。     

Production and properties of highly oriented polyoxymethylene by die‐drawing

Highly oriented monofilaments were produced by a high‐temperature die‐drawing process followed by tensile drawing. It was shown that a successful high‐speed process required high‐quality melt‐extruded rod. The mechanical properties and structure of the die‐drawn products were investigated by means of tensile and bending tests, dynamic mechanical measurements, DSC, and X‐ray diffraction. The bending modulus and the tensile strength increased with increasing draw ratio. It was also observed that at high draw ratios the γ‐dispersion peak in the dynamic mechanical tan δ curve, which is associated with main chain micro‐Brownian motion in the amorphous regions, diminishes, implying that these chains become taut. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1268–1278, 2003     

Fabrication and application of chemical vapor deposition diamond-coated drawing dies

A diamond coating has been fabricated by straight hot filament chemical vapor deposition (CVD) passing through the interior hole of the drawing die using a mixture of hydrogen and acetone as source gases. The substrates are drawing dies made by cemented carbides with large apertures (φ>2 mm), and are pre-treated by various methods including leaching Co by acid solution, scratching the substrate by diamond powder and decarburizing the WC substrate by microwave plasma. The homogeneity of coatings is estimated by scanning electron microscopy and Raman spectroscopy. The preliminary applied tests show that the adhesion strength of diamond coatings can meet the need of the practical drawing wires. As compared with the cemented carbide drawing die, the working lifetime of the diamond-coated drawing die can be increased by a factor of five to 10.     

Uniaxial drawing of poly(vinyl alcohol)/graphene oxide nanocomposites

The unique potential of graphene oxide (GO) was exploited in the nanocomposites by a simple uniaxial drawing (up to three times) of poly(vinyl alcohol) (PVA)/GO nanocomposites with a small amount loading of GO. From X-ray diffraction images, the PVA crystallites were found to be oriented parallel to the drawn direction. At the same time, exfoliated GO platelets were found to be aligned parallel to the film surface. Compared with the properties of the as-cast nanocomposites, those of the uniaxially drawn nanocomposites were found to be remarkably enhanced. For the mechanical properties, not only Young’s modulus and tensile strength but also the toughness of the nanocomposites increased by the uniaxial drawing. It was revealed that 260% increase in toughness was achieved for the drawn nanocomposite with 1% w/w GO loading. Significant suppression of the swelling in water resulted in the excellent barrier properties against water, which exceeded that of the conventional high-barrier polymer, such as poly(vinylidene chloride). We revealed that this simple, fast and environmentally friendly process of uniaxial drawing exploits the excellent properties and high aspect ratio of GO in the nanocomposites.